CN110452193A - The method that 2,5- furans dicarbaldehyde is prepared by 5 hydroxymethyl furfural - Google Patents
The method that 2,5- furans dicarbaldehyde is prepared by 5 hydroxymethyl furfural Download PDFInfo
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- CN110452193A CN110452193A CN201910698096.6A CN201910698096A CN110452193A CN 110452193 A CN110452193 A CN 110452193A CN 201910698096 A CN201910698096 A CN 201910698096A CN 110452193 A CN110452193 A CN 110452193A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
This application involves one kind by 5 hydroxymethyl furfural (5-HMF) preparation 2, the method of 5- furans dicarbaldehyde (DFF), this method comprises: 0~80 DEG C at a temperature of, in tertiary alcohols solvent, raw material 5 hydroxymethyl furfural reacts in the presence of TEMPO catalyst, organic carboxyl acid class co-catalyst, Nitrates auxiliary agent and oxidant and is converted into 2,5-furandaldehyde.By utilizing method of the invention, raw material 5 hydroxymethyl furfural (5-HMF) conversion can be obtained by target product 2 with high yield in a mild condition, 5- furans dicarbaldehyde (DFF), and process route is simple, has huge prospects for commercial application.
Description
Technical field
The present invention relates to the preparation methods of chemicals, more particularly to one kind is by 5 hydroxymethyl furfural (5-HMF) preparation 2,5-
The method of furans dicarbaldehyde (DFF).
Background technique
Fossil resource is valuable source for the survival of mankind, with the extensive utilization of fossil resource, people's lives hair
Earth-shaking variation is given birth to.But fossil resource itself also has corresponding drawback, such as the discharge of carbon dioxide, sulfur dioxide
Caused greenhouse effects and atmosphere pollution；A series of problems, such as global Oil Gas is unevenly distributed.Also, fossil resource be not take no
It is nexhaustible to the greatest extent, this research with regard to growth-promoting people to other alternative energy sources.In alternative energy source, biomass is a kind of important
Renewable energy, it is a variety of biomass-based Bio-surfactant, lubricant, plasticizer etc. can be prepared by biomass resource
Chemicals is widely used.And 2,5-furandaldehyde (DFF) is a kind of important biomass platform in Biomass-based chemicals
Molecule.2,5-furandaldehyde (DFF) is important one of the oxidization deriving product of 5 hydroxymethyl furfural (5-HMF), with aldehyde
Exemplary chemical property, 2,5-furandaldehyde (DFF) not only can be used as the essences such as medicine, macrocyclic ligand, antifungal agent, organic conductor
The intermediate of thin chemicals, but also be a kind of important furyl polymer monomer, it can be used as polyvinyl alcohol production process
In crosslinking agent, the adhesive in casting process, can be also used for manufacture electro-optical device, organic fluorescent powder and illuminator.
In addition, it prepares raw material used also as bis- (the aminomethyl)-furans of 2,5- and schiff bases.
In view of the important function and purposes of 2,5-furandaldehyde (DFF), carbohydrate especially 5- methylol is studied
Furfural (5-HMF) to the conversion in 2,5-furandaldehyde (DFF) be very meaningful.DFF traditional preparation methods are to make
It is prepared with equivalent oxidising agent such as potassium permanganate, sodium hypochlorite etc. or electrochemical oxidation process, product yield is not generally high.In order to more
Add the preparation DFF of green, researcher develops noble metal catalyst, Mn base catalyst, V-based catalyst and TEMPO series and urges
Agent etc..Chernyshev etc. uses TEMPO catalyst system in the presence of excess iodine, excess bicarbonate and trimethylpyridine,
It converts HMF to DFF (Tetrahedron Letters 58 (2017) 3517-3521).Nie etc. is using Ru/C as catalyst, toluene
Under conditions of solvent, 110 DEG C, 2.0MPa O2, available about 95% DFF yield.With the precious metal catalysts such as Pt, Pd, Au
Agent is compared, and Ru/C shows preferably activity and to the selectivity of DFF, but the reaction temperature and price of Ru catalyst still compared with
High (Pure and Applied Chemistry, 2011,84 (3): 765-777).Using vanadium phosphorus oxide in DMSO solvent,
6h is reacted at 150 DEG C, obtains 97%DFF selectivity (Applied Catalysis A:General, 2005,289 (2): 197-
204).But product is difficult to separate and difficult solvent recovery in DMSO solvent, which has limited DMSO as excellent oxidative solvent
Use scope.
Therefore, this field still need under mild reaction conditions (such as normal temperature and pressure) with simple low cost process simultaneously
And with high yield by the new method of 5 hydroxymethyl furfural (5-HMF) preparation 2,5-furandaldehyde (DFF).
Summary of the invention
In view of above-mentioned, the object of the present invention is to provide under mild reaction conditions (such as normal temperature and pressure) with simple low
Cost process and the new method for preparing 2,5-furandaldehyde (DFF) by 5 hydroxymethyl furfural (5-HMF) with high yield.
For this purpose, the present invention provides a kind of method by 5 hydroxymethyl furfural preparation 2,5-furandaldehyde, the method
Include: 0~80 DEG C at a temperature of, in tertiary alcohols solvent, raw material 5 hydroxymethyl furfural is in TEMPO catalyst, organic carboxyl acid
It reacts in the presence of class co-catalyst, Nitrates auxiliary agent and oxidant and is converted into 2,5-furandaldehyde,
Wherein, the TEMPO catalyst is selected from one of catalyst 1-6 having following structure or a variety of:
In preferred embodiments, the organic carboxyl acid class co-catalyst is C1-C6 organic carboxyl acid, preferably described to have
Machine carboxylic acids co-catalyst is selected from one of the following terms or a variety of: oxalic acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, penta
Acid, caproic acid, hexanedioic acid, furancarboxylic acid, furandicarboxylic acid, levulic acid, succinic acid and malonic acid.
In preferred embodiments, the Nitrates auxiliary agent is to be selected from one of the following terms or a variety of: Cu
(NO3)2、Fe(NO3)3、Mn(NO3)2、Al(NO3)3With Zn (NO3)2。
In preferred embodiments, the tertiary alcohols solvent is to be selected from one of the following terms or a variety of: the tert-butyl alcohol,
The pure and mild 2- methyl of 2- methyl-amyl- 2- alcohol, 3- methyl-amyl- 3--butyl- 2- alcohol.
In preferred embodiments, the oxidant is selected from one of the following terms or a variety of: air, oxygen,
Hydrogen peroxide, peroxide salt and hypohalite；The preferably described reaction carries out under the air or oxygen atmosphere of 0.1~1.0MPa.
In preferred embodiments, it is described reaction 0~50 DEG C at a temperature of carry out；The preferably described reaction 10~
It is carried out at a temperature of 30 DEG C.
In preferred embodiments, the time of the reaction is 1~96h；It is preferred that the time of the reaction is 1~36h.
In preferred embodiments, the quality of the TEMPO catalyst and the raw material 5- hydroxymethylfurfural that use
Than being 0.01: 1~1: 1.
In preferred embodiments, the organic carboxyl acid class co-catalyst and the raw material 5 hydroxymethyl furfural used
Mass ratio be 0.01: 1~2: 1.
In preferred embodiments, the matter of the Nitrates auxiliary agent and the raw material 5- hydroxymethylfurfural that use
Amount is than being 0.01: 1~1: 1.
By the present invention in that with special catalyst cheap and easy to get, co-catalyst and Nitrates auxiliary agent, with 5- methylol
Furfural (5-HMF) is raw material, and in tertiary alcohols solvent, catalysis oxidation obtains 2,5-furandaldehyde (DFF).Method of the invention
2,5-furandaldehyde (DFF) can be obtained under the conditions of extremely mild (such as normal temperature and pressure).The method of the present invention uses the tertiary alcohol
Class solvent and organic acid assistant, can highly selective in a mild condition and yield, simple process, have it is huge
Industrial application value.
Specific embodiment
The present invention provides a kind of methods by 5 hydroxymethyl furfural preparation 2,5-furandaldehyde, which comprises
0~80 DEG C at a temperature of, in tertiary alcohols solvent, the 5 hydroxymethyl furfural as raw material is in TEMPO catalyst, organic carboxylic
It reacts in the presence of acids co-catalyst, Nitrates auxiliary agent and oxidant and is converted into 2,5-furandaldehyde.
In the method for the invention, the TEMPO catalyst used is one in the catalyst 1-6 having following structure
Kind is a variety of:
Such TEMPO catalyst is known in the art, and can be commercially available, and catalyst 1 as escribed above can
To derive from Ann Kyrgyzstan company (98% purity).Moreover, such TEMPO catalyst sometimes can also be respectively with active shape below
Formula (i.e. radical form) occurs, obtains or uses:
TEMPO catalyst is catalyst of the efficient catalysis oxidation alcohol to aldehyde, and the oxygen of the alcohol under temperate condition may be implemented
Change, exemplary catalyst is shown in the reaction mechanism is as follows:
In the method for the invention, it is preferable that the TEMPO catalyst is with raw material 5 hydroxymethyl furfural quality dosage
0.01~1 times of amount uses (i.e. the mass ratio of the two is 0.01: 1~1: 1).If catalyst amount is too low, can to react
Process is lasting too long, and damages its and industrialize meaning；If catalyst amount is too high, can process costs be increased, can also damage
Its industrialization meaning of evil.
In the method for the invention, in order in high yield by 5 hydroxymethyl furfural catalysis oxidation be target product 2,5- furans
Dicarbaldehyde is needed using organic carboxyl acid class co-catalyst.The use of organic carboxyl acid class co-catalyst mainly assist dehydrating agent with
Nitrogen oxides intermediate is formed, the acquisition of reaction product is conducive to during reaction, does not use organic carboxyl acid class co-catalyst
And TEMPO catalyst is used alone and will lead to the extension in reaction time and the decline of reaction yield.
In the method for the invention, the organic carboxyl acid class co-catalyst used is preferably C1-C6 organic carboxyl acid, more preferably
Ground is selected from one of the following terms or a variety of: oxalic acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, two
Acid, furancarboxylic acid, furandicarboxylic acid, levulic acid, succinic acid and malonic acid.
In the method for the invention, it is preferable that organic carboxyl acid class co-catalyst is with raw material 5 hydroxymethyl furfural quality dosage
0.01~2 times of amount use (mass ratio both i.e. is 0.01: 1~2: 1).If organic carboxylic acids co-catalyst dosage is too
It is low, reaction process can be made to continue too long and target aldehyde product cannot be obtained；If organic carboxylic acids co-catalyst dosage is too
Height can make process costs increase, and can also damage it and industrialize meaning.
In the method for the invention, it is preferable that the Nitrates auxiliary agent used can be selected from one of the following terms
It is or a variety of: Cu (NO3)2、Fe(NO3)3、Mn(NO3)2、Al(NO3)3With Zn (NO3)2.It is not only restricted to specific theory, it is believed that nitric acid
The effect of salt analog assistant is to make have the reaction system of above-mentioned catalyst and co-catalyst more stable, while the nitrate anion of high-valence state
With oxidisability, nitrogen oxides can be quickly generated, promotes the progress of methylol oxidation reaction.So that reaction can be mild
Under the conditions of carry out.
In the method for the invention, it is preferable that the Nitrates auxiliary agent is used with the raw material 5- hydroxymethylfurfural quality
0.01~1 times of amount of amount uses (i.e. the mass ratio of the two is 0.01: 1~1: 1).If Nitrates auxiliary dosage is too low,
It is slower to will cause reaction speed；If Nitrates auxiliary dosage is too high, Peroxidation Product acquisition will lead to, reduce product selection
Property.
In the method for the invention, using tertiary alcohols solvent, which not only remains alcohols solvent to reaction
The high-efficiency dissolution of substrate and product, simultaneously because tertiary alcohols solvent is difficult to further be aoxidized, it is possible to reduce to catalyst
The toxic action of TEMPO.In the present invention, tertiary alcohols solvent is not particularly limited, it is preferable that the tertiary alcohols solvent used
It can be and be selected from one of the following terms or a variety of: the pure and mild 2- first of the tert-butyl alcohol, 2- methyl-amyl- 2- alcohol, 3- methyl-amyl- 3-
Base-butyl- 2- alcohol.
In the method for the invention, used oxidant is not particularly limited, it is preferable that the oxidant used can be with
It is to be selected from one of the following terms or a variety of: air, oxygen, hydrogen peroxide, peroxide salt and hypohalite.Although in the present invention
Method in refer to and carrying out in the presence of an oxidizer, but in fact, since the method for the present invention completely can be in air atmosphere
Such as the oxidant for carrying out in open reactor, therefore referring in the present invention is to a certain degree it is also assumed that be to be not present
's.In other words, the method for the present invention, which can be, carries out in the presence of anaerobic agent.
In the method for the invention, it is preferable that when using air or oxygen as when oxidant, the reaction can be direct
Directly carried out under air or oxygen atmosphere, can also by by oxygen or oxygen by bubbling mode be passed through in reaction system into
Row, or can also 0.1~1.0MPa air or oxygen atmosphere under (such as by utilize closed reactor) progress.
Method of the invention can 0~50 DEG C at a temperature of carry out, preferably react 10~50 DEG C at a temperature of into
Row；More preferably it is described reaction 20~30 DEG C at a temperature of carry out.
In the method for the invention, the reaction time is not particularly limited, it is preferable that the time of the reaction be 1~
96h；It is preferred that the time of the reaction is 1~36h.
Implementation process of the present invention is described further combined with specific embodiments below.As described below is only that the present invention is preferable
Specific embodiment, but scope of protection of the present invention is not limited thereto.
In the examples below, if not otherwise specified, the raw materials and reagents used can be bought from traditional Chinese medicines reagent,
And it is used as former state under not after further treatment with its；The reactor Shrek pipe used can be bought from Xin Weier, efficiently
Liquid chromatographic detection can be bought from Shimadzu.
Embodiment 1
In 10mL Shrek pipe, it is packed into 126mg 5 hydroxymethyl furfural (5-HMF), 11 mg catalyst 1 and 24mg Cu
(NO3)2, 60mg CH is then added3COOH the and 2mL tert-butyl alcohol, and in atmospheric oxygen atmosphere, in magnetic agitation (stirring rate
30 DEG C of reaction 36h are heated to for water-bath under 800r/min).After the reaction was completed, it samples and is sent to high-efficient liquid phase color under stirring
(HPLC) detection is composed, wherein testing conditions are as follows: Hitachi L2000HPLC System, Alltech C18 column, mobile phase
CH3OH∶H2O=20: 80；Flow velocity: 1.0mL/min, column temperature: 30 DEG C, detector: DAD, Detection wavelength: 264nm.It is examined by HPLC
It surveys, the yield of product furans dicarbaldehyde (DFF) is 88.90%, and its purity is 99%.
Embodiment 2
Specific reaction process and detection method are same as Example 1, only will be that the tert-butyl alcohol is changed to tertiary hexanol, as a result institute
Obtaining primary product is 2,5-furandaldehyde (DFF), and yield is 81.46%, and its purity is 99.5%.
Embodiment 3
Specific reaction process and detection method are same as Example 1, the tert-butyl alcohol are only changed to tert-pentyl alcohol, as a result institute
Obtaining primary product is 2,5-furandaldehyde (DFF), and yield is 78.51%, and its purity is 98%.
Embodiment 4
Specific reaction process and detection method are same as Example 1, catalyst 1 are only changed to catalyst 2, as a result
Gained primary product is 2,5-furandaldehyde (DFF), and yield is 83.89%, and its purity is 97.8%.
Embodiment 5
Specific reaction process and detection method are same as Example 1, catalyst 1 are only changed to catalyst 3, as a result
Gained primary product is 2,5-furandaldehyde (DFF), and yield is 75.22%, and its purity is 98.3%.
Embodiment 6
Specific reaction process and detection method are same as Example 1, catalyst 1 are only changed to catalyst 5, as a result
Gained primary product is 2,5-furandaldehyde (DFF), and yield is 90.71%, and its purity is 98.2%.
Embodiment 7
Specific reaction process and detection method are same as Example 1, only by CH3COOH is changed to oxalic acid, as a result institute
Obtaining primary product is 2,5-furandaldehyde (DFF), and yield is 78.54%, and its purity is 96.9%.
Embodiment 8
Specific reaction process and detection method are same as Example 1, only by CH3COOH is changed to malonic acid, as a result
Gained primary product is 2,5-furandaldehyde (DFF), and yield is 88.99%, and its purity is 98.5%.
Embodiment 9
Specific reaction process and detection method are same as Example 1, only by CH3COOH is changed to succinic acid, as a result
Gained primary product is 2,5-furandaldehyde (DFF), and yield is 70.34%, and its purity is 97.8%.
Embodiment 10
Specific reaction process and detection method are same as Example 1, only by CH3COOH is changed to citric acid, as a result
Gained primary product is 2,5-furandaldehyde (DFF), and yield is 86.10%, and its purity is 99.1%.
Embodiment 11
Specific reaction process and detection method are same as Example 1, only by Cu (NO3)2It is changed to Fe (NO3)3.As knot
Primary product obtained by fruit is 2,5-furandaldehyde (DFF), and yield is 75.72%, and its purity is 98.7%.
Embodiment 12
Specific reaction process and detection method are same as Example 1, only by Cu (NO3)2It is changed to Mn (NO3)2.As knot
Primary product obtained by fruit is 2,5-furandaldehyde (DFF), and yield is 61.88%, and its purity is 98.7%.
Embodiment 13
Specific reaction process and detection method are same as Example 1, only by Cu (NO3)2It is changed to Al (NO3)3.As knot
Primary product obtained by fruit is 2,5-furandaldehyde (DFF), and yield is 85.05%, and its purity is 98.3%.
Embodiment 14
Specific reaction process and detection method are same as Example 1, and oxidant is only changed to KMnO from atmospheric oxygen4,
Gained primary product is 2,5-furandaldehyde (DFF) as a result, and yield is 81.77%, and its purity is 97.7%.
Embodiment 15
Specific reaction process and detection method are same as Example 1, and oxidant is only changed to hydrogen peroxide from atmospheric oxygen,
Gained primary product is 2,5-furandaldehyde (DFF) as a result, and yield is 77.50%, and its purity is 98.1%.
Embodiment 16
Specific reaction process and detection method are same as Example 1, and oxidant is only changed to air from atmospheric oxygen, make
It is 2,5-furandaldehyde (DFF) for primary product obtained by result, and yield is 80.31%, and its purity is 97.9%.
Embodiment 17
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction time of furans dicarbaldehyde (DFF) is changed to 12h from 36h, and gained primary product is 2,5-furandaldehyde as a result
(DFF), and yield is 76.97%, and its purity is 99.7%.
Embodiment 18
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction time of furans dicarbaldehyde (DFF) is changed to for 24 hours from 36h, and gained primary product is 2,5-furandaldehyde as a result
(DFF), and yield is 88.42%, and its purity is 97.8%.
Embodiment 19
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction temperature of furans dicarbaldehyde (DFF) is changed to 10 DEG C from 30 DEG C, and gained primary product is 2,5-furandaldehyde as a result
(DFF), and yield is 74.92%, and its purity is 97.6%.
Embodiment 20
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5- furan
The reaction temperature of dicarbaldehyde of muttering (DFF) is changed to 40 DEG C from 30 DEG C, and gained primary product is 2,5-furandaldehyde as a result
(DFF), and yield is 69.34%, and its purity is 98.3%.
Embodiment 21
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction temperature of furans dicarbaldehyde (DFF) is changed to 20 DEG C from 30 DEG C, and gained primary product is 2,5-furandaldehyde as a result
(DFF), and yield is 78.27%, and its purity is 99.7%.
Embodiment 22
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The oxygen reaction pressure of furans dicarbaldehyde (DFF) is changed to 0.5 Mpa from normal pressure, and gained primary product is 2,5- furans as a result
Dicarbaldehyde (DFF), and yield is 89.61%, and its purity is 97.6%.
Embodiment 23
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The oxygen reaction pressure of furans dicarbaldehyde (DFF) is changed to 2 Mpa from normal pressure, and gained primary product is 2,5- furans two as a result
Formaldehyde (DFF), and yield is 90.58%, and its purity is 99.1%.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright range is defined by the following claims.
Claims (10)
1. a kind of method by 5 hydroxymethyl furfural preparation 2,5-furandaldehyde, which comprises in 0~80 DEG C of temperature
Under, in tertiary alcohols solvent, raw material 5 hydroxymethyl furfural is helped in TEMPO catalyst, organic carboxyl acid class co-catalyst, Nitrates
It is reacted in the presence of agent and oxidant and is converted into 2,5-furandaldehyde,
Wherein, the TEMPO catalyst is selected from one of catalyst 1-6 having following structure or a variety of:
2. the method according to claim 1, wherein the organic carboxyl acid class co-catalyst is the organic carboxylic of C1-C6
Acid, the preferably described organic carboxyl acid class co-catalyst are selected from one of the following terms or a variety of: oxalic acid, citric acid, formic acid,
Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, adipic acid, furancarboxylic acid, furandicarboxylic acid, levulic acid, succinic acid and malonic acid.
3. the method according to claim 1, wherein the Nitrates auxiliary agent is one in the following terms
Kind is a variety of: Cu (NO3)2、Fe(NO3)3、Mn(NO3)2、Al(NO3)3With Zn (NO3)2。
4. the method according to claim 1, wherein the tertiary alcohols solvent is selected from one of the following terms
It is or a variety of: the pure and mild 2- methyl of the tert-butyl alcohol, 2- methyl-amyl- 2- alcohol, 3- methyl-amyl- 3--butyl- 2- alcohol.
5. the method according to claim 1, wherein the oxidant is to be selected from one of the following terms or more
Kind: air, oxygen, hydrogen peroxide, peroxide salt and hypohalite；Air or oxygen of the preferably described reaction in 0.1~1.0MPa
Atmosphere encloses lower progress.
6. the method according to claim 1, wherein it is described reaction 0~50 DEG C at a temperature of carry out；Preferably
It is described reaction 10~30 DEG C at a temperature of carry out.
7. the method according to claim 1, wherein the time of the reaction is 1~96h；It is preferably described anti-
The time answered is 1~36h.
8. the method according to claim 1, wherein the TEMPO catalyst used and the raw material 5- hydroxyl
The mass ratio of methyl furfural is 0.01: 1~1: 1.
9. the method according to claim 1, wherein the organic carboxyl acid class co-catalyst used and the original
The mass ratio for expecting 5 hydroxymethyl furfural is 0.01: 1~2: 1.
10. the method according to claim 1, wherein the Nitrates auxiliary agent used and the raw material 5-
The mass ratio of hydroxymethylfurfural is 0.01: 1~1: 1.
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| CN111269202A (en) * | 2020-02-26 | 2020-06-12 | 南京林业大学 | Preparation method of 2, 5-furan diformaldehyde under illumination condition |
| CN112661729A (en) * | 2020-12-23 | 2021-04-16 | 东莞理工学院 | Application of nitrate-assisted carbon catalytic system in preparation of 2, 5-furandicarboxaldehyde by catalytic conversion of 5-hydroxymethylfurfural |
| CN113559930A (en) * | 2021-07-26 | 2021-10-29 | 南京林业大学 | Preparation method and application of solid catalyst taking sodium lignosulfonate as carrier |
| CN114481170A (en) * | 2022-01-24 | 2022-05-13 | 吉林大学 | Method for linear paired electrochemical synthesis of furoic acid from furfural |
| CN115850213A (en) * | 2022-11-11 | 2023-03-28 | 南京师范大学 | Method for efficiently preparing 2,5-furandicarboxaldehyde |
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| CN111269202A (en) * | 2020-02-26 | 2020-06-12 | 南京林业大学 | Preparation method of 2, 5-furan diformaldehyde under illumination condition |
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| CN113559930A (en) * | 2021-07-26 | 2021-10-29 | 南京林业大学 | Preparation method and application of solid catalyst taking sodium lignosulfonate as carrier |
| CN113559930B (en) * | 2021-07-26 | 2023-05-23 | 南京林业大学 | Preparation method and application of solid catalyst taking sodium lignin sulfonate as carrier |
| CN114481170A (en) * | 2022-01-24 | 2022-05-13 | 吉林大学 | Method for linear paired electrochemical synthesis of furoic acid from furfural |
| CN114481170B (en) * | 2022-01-24 | 2023-08-15 | 吉林大学 | Method for synthesizing furoic acid by furfural in linear paired electrochemical manner |
| CN115850213A (en) * | 2022-11-11 | 2023-03-28 | 南京师范大学 | Method for efficiently preparing 2,5-furandicarboxaldehyde |
| CN115850213B (en) * | 2022-11-11 | 2024-02-06 | 南京师范大学 | Method for efficiently preparing 2, 5-furan dicarboxaldehyde |
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